Water → (1alpha,5alpha,17beta)-17-(Acetyloxy)-1-methylandrostan-3-one

HRID 1415847Notes

Reaction equation

HRID 1415847 reaction equation
[C:1]([O:4][C@H:5]1[CH2:10][CH2:9][C@H:8]2[C@H:11]3[C@H:21]([CH2:22][CH2:23][C@:6]12[CH3:7])[C@:19]1([CH3:20])[CH:14]([CH2:15][C:16](=[O:24])[CH:17]=[CH:18]1)[CH2:13][CH2:12]3)(=[O:3])[CH3:2].[CH3:25][Al](C)C.O>C(OCC)(=O)C.C1(C)C=CC=CC=1.[Cu]Br>[C:1]([O:4][C@H:5]1[CH2:10][CH2:9][C@H:8]2[C@H:11]3[C@H:21]([CH2:22][CH2:23][C@:6]12[CH3:7])[C@:19]1([CH3:20])[C@H:14]([CH2:15][C:16](=[O:24])[CH2:17][C@@H:18]1[CH3:25])[CH2:13][CH2:12]3)(=[O:3])[CH3:2]

Participants

7

Reactant 3

HCID 962WaterHCID 10969589HCID 10969589, compoundHCID 16682925Trimethylaluminum

Product 1

HCID 107497(1alpha,5alpha,17beta)-17-(Acetyloxy)-1-methylandrostan-3-one

Reagents, catalysts & solvents 3

HCID 24593copper(I) bromideCatalystHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent2×

Procedure

Variant 2 (in ethyl acetate : 66.1 g (0.2 mol) of 17β-acetoxy-androst-1-en-3-one is dissolved in 350 ml of dry ethyl acetate and mixed with 1.43 g (10 mmol) of copper(I) bromide. 188 ml (0.22 mol) of a 10% solution of trimethyl aluminum in toluene is added over 15 minutes to the reaction under nitrogen atmosphere, so that the temperature does not rise above 25° C. Then it is stirred for 30 minutes more. For hydrolysis, 15 ml of water is added to the reaction and stirred for 40 minutes more. The solid is suctioned off and absorptively precipitated three times, each with 200 ml of dioxane. After concentration by evaporation of the combined organic phases, 65.6 g of 17β-acetoxy-1α-methyl-androstan-3-one (95% of theory) of a melting point of 181° C. is obtained.

Workup

  1. customdoes not rise above 25° C
  2. additionis added to the reaction
  3. stirringstirred for 40 minutes more
  4. customabsorptively precipitated three times
  5. concentrationAfter concentration
  6. customby evaporation of the combined organic phases, 65.6 g of 17β-acetoxy-1α-methyl-androstan-3-one (95% of theory) of a melting point of 181° C.
  7. customis obtained

Sources & evidence

ORD record
ord-b77a00f7c17343e6b64f6e2434e25cbe
Source dataset
uspto-grants-1999_06
Patent number
US05908944

Reaction notes

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